KR100397794B1 - Process for Preparing Aliphatic Acid Alkylester and Aliphatic Acid Ester Glycerin Carbonate - Google Patents
Process for Preparing Aliphatic Acid Alkylester and Aliphatic Acid Ester Glycerin Carbonate Download PDFInfo
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- KR100397794B1 KR100397794B1 KR10-2000-0059048A KR20000059048A KR100397794B1 KR 100397794 B1 KR100397794 B1 KR 100397794B1 KR 20000059048 A KR20000059048 A KR 20000059048A KR 100397794 B1 KR100397794 B1 KR 100397794B1
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- Prior art keywords
- fatty acid
- carbonate
- alcohol
- esters
- catalyst
- Prior art date
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- -1 Ester Glycerin Carbonate Chemical class 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002253 acid Substances 0.000 title description 6
- 125000001931 aliphatic group Chemical group 0.000 title description 3
- 125000005907 alkyl ester group Chemical group 0.000 title 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 69
- 239000000194 fatty acid Substances 0.000 claims abstract description 69
- 229930195729 fatty acid Natural products 0.000 claims abstract description 69
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 22
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 16
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 150000005677 organic carbonates Chemical class 0.000 claims abstract description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010457 zeolite Substances 0.000 claims abstract description 9
- 239000002815 homogeneous catalyst Substances 0.000 claims abstract description 7
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 3
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 150000003626 triacylglycerols Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- 229940055577 oleyl alcohol Drugs 0.000 claims description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 abstract description 7
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000015227 regulation of liquid surface tension Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229960004838 phosphoric acid Drugs 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
본 발명은 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트의 동시 제조방법에 관한 것이다. 본 발명은 알코올에 트리글리세라이드와 유기 카보네이트를 1:1의 비율(w/w)로 용해시키고, 균질촉매, 합성 지오라이트 촉매, 이온교환수지 촉매 또는 4가 알킬 암모늄염 촉매를 전체 반응 혼합물에 대하여 0.01 내지 10%(w/w) 첨가하여, 30 내지 200℃의 온도에서 0.5 내지 8시간 반응시켜, 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 동시에 제조하는 공정을 포함한다. 본 발명에 의하면, 비독성, 비휘발성의 지방산 알킬에스테르를 간단한 공정으로 경제적, 효율적으로 생산할 수 있으며, 계면활성이 적은 전기 화합물의 효능을 향상시키기 위해 이용되는 분산제로서 환경친화적인 지방산 에스테르 글리세린 카보네이트를 동시에 제조할 수 있다.The present invention relates to a process for the simultaneous preparation of fatty acid alkyl esters and fatty acid esters, glycerin carbonate. The present invention dissolves triglyceride and organic carbonate in alcohol in a ratio of 1: 1 (w / w), and homogeneous catalyst, synthetic zeolite catalyst, ion exchange resin catalyst or tetravalent alkyl ammonium salt catalyst in 0.01 to the whole reaction mixture. To 10% (w / w), and reacted at a temperature of 30 to 200 ° C. for 0.5 to 8 hours, thereby simultaneously producing a fatty acid alkyl ester and a fatty acid ester glycerin carbonate. According to the present invention, a non-toxic, nonvolatile fatty acid alkyl ester can be produced economically and efficiently in a simple process, and an environmentally friendly fatty acid ester glycerin carbonate is used as a dispersant used to improve the efficacy of an electric compound having low surfactant activity. It can be produced at the same time.
Description
본 발명은 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트의 동시 제조방법에 관한 것이다. 좀 더 구체적으로, 본 발명은 알코올에 동일 중량의 트리글리세라이드 및 유기 카보네이트를 용해시키고, 균질촉매, 합성 지오라이트 촉매, 이온교환수지 촉매 또는 4가 알킬 암모늄염 촉매를 첨가하여 반응시켜, 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 동시에 제조하는 방법에 관한 것이다.The present invention relates to a process for the simultaneous preparation of fatty acid alkyl esters and fatty acid esters, glycerin carbonate. More specifically, the present invention dissolves an equal weight of triglyceride and organic carbonate in alcohol, and reacts by adding a homogeneous catalyst, a synthetic zeolite catalyst, an ion exchange resin catalyst or a tetravalent alkyl ammonium salt catalyst to react with a fatty acid alkyl ester. It relates to a process for producing fatty acid ester glycerin carbonate simultaneously.
지방산 알킬에스테르는 환경에 무해한 비독성, 비휘발성의 장점 때문에 청정 디젤 연료의 첨가제로 주목을 끌고 있으나, 저온에서 침전되고 낮은 계면활성을 가지므로, 이미드, 아미드, 아민계와 같은 질소함유 분산제와 함께 널리 사용되고 있다(참조: PCT/EP 1997/05106; WO 95/33805; 미국특허 4,185,594; 미국특허 4,428,182 등). 그러나, 이런 질소함유 분산제는 NOx등의 공해물질을 배출하므로,순수한 탄화수소 및 산소만을 함유한 환경에 무해한 분산제를 개발하려는 노력이 계속되어 왔다.Fatty acid alkyl esters have attracted attention as additives for clean diesel fuels because of their non-toxic and non-volatile properties, which are harmless to the environment, but because they precipitate at low temperatures and have low surfactant activity, Widely used together (see PCT / EP 1997/05106; WO 95/33805; US Patent 4,185,594; US Patent 4,428,182, etc.). However, since these nitrogen-containing dispersants emit pollutants such as NOx, efforts have been made to develop dispersants that are harmless to the environment containing only pure hydrocarbons and oxygen.
일반적으로, 지방산 알킬에스테르는 트리글리세라이드와 알코올의 에스테르 교환반응으로 합성되나(참조: 독일특허 1,901,434; 유럽특허 301,634; 프랑스특허 1,584,584; 미국특허 3,852), 부산물인 글리세린의 비용해성(친수성)에 의해 층분리, 고체촉매 사용시 응집 등으로 반응시간이 오래 걸리고 수율이 낮은 단점이 있으므로, 실제 공정에서는 알코올의 농도를 높여 글리세린의 친유성 반응물에 대한 용해도를 높이거나 반응 후 이를 제거하는 공정을 채택하고 있다. 그러나, 이와 같은 공정으로 반응성을 높이는 것은 한계가 있으므로, 글리세린 비용해성의 문제점을 극복할 수 있는 새로운 공정의 개발이 요구되었다.Generally, fatty acid alkyl esters are synthesized by transesterification of triglycerides with alcohols (see German Patent 1,901,434; European Patent 301,634; French Patent 1,584,584; United States Patent 3,852), but the layer is formed by the insolubility (hydrophilicity) of the byproduct glycerin. Due to the disadvantage that the reaction takes a long time and yield is low due to the flocculation and the use of a solid catalyst, the actual process adopts a process of increasing the concentration of alcohol to increase the solubility of the glycerol lipophilic reactant or removing it after the reaction. However, since there is a limit to increase the reactivity in such a process, it has been required to develop a new process that can overcome the problem of glycerin insoluble.
한편, 분자내에 에스테르기, 헤테로 사이클 카보네이트의 극성 그룹들 및 지방산 탄소사슬로 이루어진 비극성 그룹을 동시에 가지고 있는 지방산 에스테르 글리세린 카보네이트는 카보네이트의 높은 정전기적 인력으로 인하여, 친유성이 강하면서도 높은 계면활성을 가지는 특이한 물질로, 휘발유 및 경유등 연료에 첨가하는 경우, 분자내 극성 성분의 작용으로 윤활성이 높은 분산제 역할을 하며, 아울러, 분자 내부에 5개의 반응성 산소를 함유하고 있어 우수한 산소 첨가제로 작용하는 다기능성 분자이다. 그러나, 이 물질의 합성은 수율이 낮고, 혼합액의 응용성이 낮아, 좋은 특성에도 불구하고 현재까지 실질적으로 상용화되지 못하고 있는 실정이다(참조: 독일특허 3,937,116; 미국 특허 2,979,514; WO 93/0911).On the other hand, fatty acid ester glycerin carbonate which has an ester group, a polar group of heterocycle carbonate and a non-polar group consisting of fatty acid carbon chain in the molecule has a high lipophilic and high surface activity due to the high electrostatic attraction of the carbonate. As a unique substance, when added to fuels such as gasoline and diesel, it acts as a highly lubricating dispersant due to the action of polar components in the molecule, and also contains five reactive oxygens inside the molecule, which makes it an excellent oxygen additive. It is a molecule. However, the synthesis of this material is low in yield, low in applicability of the mixed liquor, and has not been substantially commercialized to date despite good properties (see German Patent 3,937,116; US Patent 2,979,514; WO 93/0911).
따라서, 비독성, 비휘발성의 지방산 알킬에스테르를 간단한 공정으로 효율적으로 제조할 수 있고, 낮은 계면활성의 전기 화합물의 응용을 넓히기 위하여, 환경친화적 분산제인 지방산 에스테르 글리세린 카보네이트를 제조하는 기술을 개발하여야 할 필요성이 끊임없이 대두되었다.Therefore, in order to efficiently manufacture non-toxic and nonvolatile fatty acid alkyl esters in a simple process, and to expand the application of low-interactive electrical compounds, it is necessary to develop a technique for producing fatty acid ester glycerin carbonate, which is an environmentally friendly dispersant. Necessity arose constantly.
이에, 본 발명자들은 높은 수득율을 가진 비독성, 비휘발성의 지방산 알킬에스테르와 낮은 계면활성을 가진 전기 화합물을 사용하기 위해 환경친화적 분산제인 지방산 에스테르 글리세린 카보네이트를 경제적으로 제조할 수 있는 기술을 확립하고자 예의 연구노력한 결과, 트리글리세라이드와 알코올간 에스테르 교환반응에 카보네이트 함유분자를 혼합하여 반응시킨 결과, 고순도, 고수율의 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트가 동시에 제조될 수 있음을 확인하고, 본 발명을 완성하게 되었다.Accordingly, the present inventors have made great efforts to establish a technique that can economically prepare an environmentally friendly dispersant fatty acid ester glycerin carbonate to use a non-toxic, nonvolatile fatty acid alkyl ester having a high yield and an electric compound having a low surface activity. As a result of the research, the result of reacting a mixture of carbonate-containing molecules in the transesterification reaction between triglyceride and alcohol, confirmed that high-purity, high yield fatty acid alkyl ester and fatty acid ester glycerin carbonate can be prepared at the same time, and completed the present invention. Was done.
결국, 본 발명의 주된 목적은 높은 수율과 고순도의 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 동시 제조하는 방법을 제공하는 것이다.After all, the main object of the present invention is to provide a method for the simultaneous production of high yield and high purity fatty acid alkyl ester and fatty acid ester glycerin carbonate.
본 발명의 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트의동시 제조방법은, 알코올에 트리글리세라이드와 유기 카보네이트를 1:1의 비율(w/w)로 용해시키고, 균질촉매, 합성 지오라이트 촉매, 이온교환수지 촉매 또는 4가 알킬 암모늄염 촉매를 전체 반응 혼합물에 대하여 0.01 내지 10%(w/w) 첨가하며, 알코올의 양은 트리글리세라이드에 대하여 1 내지 40배(몰비), 바람직하게는 2 내지 20배로 사용하였고, 30 내지 200℃, 바람직하게는 60 내지 120℃에서, 0.5 내지 8시간 반응시켜 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 동시에 제조하는 공정을 포함한다. 이때, 알코올로서는 카르복실기, 다른 알코올기, 에폭시기 또는 에테르기를 가지는 포화 또는 불포화 탄화수소를 사용하는데, 예를 들면, 에틸 알코올, 프로필 알코올, 노말-부틸 알코올, 라우릴 알코올 또는 올레일 알코올을 사용하며, 트리글리세라이드로서는 카르복실기, 알코올기, 에폭시기, 에테르기, 숙신기, 아민기 또는 아미드기를 가지는 포화 또는 불포화 탄화수소를 사용하는데, 예를 들면, 팜유, 해바라기 기름 또는 피마자 기름를 사용하고, 또한, 유기카보네이트로서는 디알킬 카보네이트, 디페닐 카보네이트 또는 알킬렌 카보네이트를 사용한다.Simultaneous preparation method of fatty acid alkyl ester and fatty acid ester glycerin carbonate of the present invention dissolves triglyceride and organic carbonate in alcohol in a ratio of 1: 1 (w / w), homogeneous catalyst, synthetic zeolite catalyst and ion exchange resin. A catalyst or a tetravalent alkyl ammonium salt catalyst was added in an amount of 0.01 to 10% (w / w) based on the total reaction mixture, and the amount of alcohol was used in an amount of 1 to 40 times (molar ratio), preferably 2 to 20 times, relative to triglycerides, And a step of simultaneously producing a fatty acid alkyl ester and a fatty acid ester glycerin carbonate by reacting at 30 to 200 ° C, preferably 60 to 120 ° C for 0.5 to 8 hours. At this time, a saturated or unsaturated hydrocarbon having a carboxyl group, another alcohol group, an epoxy group or an ether group is used as the alcohol, for example, ethyl alcohol, propyl alcohol, normal-butyl alcohol, lauryl alcohol or oleyl alcohol, and triglycol. As the ceride, a saturated or unsaturated hydrocarbon having a carboxyl group, an alcohol group, an epoxy group, an ether group, a succinic group, an amine group or an amide group is used. Carbonate, diphenyl carbonate or alkylene carbonate.
한편, 균질촉매로는 황산, 파라-톨루엔 설포닉산, 인산, 황산아연, 황산마그네슘, 황산망간염, NaOH, KOH, EtONa, MeONa, KHCO3또는 K2CO3를 사용하며, 합성 지오라이트 촉매로서는 X형, Y형 또는 A형 지오라이트를 사용하고, 이온교환수지로서는 수소, 마그네슘(Mg), 망간(Mn), 아연(Zn), 수산기(OH-), 비카보네이트(HCO3 -),HSO4 -또는 카보네이트 (CO3 2-)를 포함하는 이온교환수지를 사용하며, 4가 알킬 암모늄염은 수산기, 브롬 또는 염소 이온을 가지는 암모늄염을 사용한다.On the other hand, as a homogeneous catalyst, sulfuric acid, para-toluene sulfonic acid, phosphoric acid, zinc sulfate, magnesium sulfate, manganese sulfate, NaOH, KOH, EtONa, MeONa, KHCO 3 or K 2 CO 3 are used. using the X-type, Y-type or a-type geometry light, ion-exchange resins include hydrogen, and magnesium (Mg), manganese (Mn), zinc (Zn), hydroxyl (OH -), bicarbonate (HCO 3 -), HSO 4 - or a carbonate using an ion exchange resin containing a (CO 3 2-), and the 4-alkyl ammonium salt is used an ammonium salt having a hydroxyl group, a chlorine or bromine ion.
이하, 실시예에 의하여 본 발명을 보다 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .
실시예 1: 지방산 메틸에스테르와 지방산 에스테르 글리세린 카보네이트 동시 제조 Example 1 : Simultaneous preparation of fatty acid methyl ester and fatty acid ester glycerin carbonate
냉각 환류기와 교반기를 설비한 500ml 용량의 반응기에 대두에서 추출한 트리글리세라이드 90g, 촉매인 황산(98%) 1g을 주입하였다. 이어, 메틸알코올 64g과 디메틸카보네이트 90g을 가한 후, 반응기의 온도를 90℃으로 유지하고, 메틸알코올을 환류시키며 반응을 4시간 지속시켰다. 4시간 경과후 반응을 종료시킨 다음, 반응액을 분액 깔대기에 넣고 증류수를 이용하여 촉매와 글리세린 카보네이트를 제거하여 얻어진 친유성 유기액은 황산 마그네슘으로 잔류하는 물을 제거한 후, 메틸알코올과 디메틸카보네이트를 증류시켰다. 최종 회수된 지방산 메틸에스테르를 포함한 용액은 비극성 미세관을 장착한 기체 크로마토그래피(gas chromatography) 분석기를 이용하여 순도분석을 수행하였다. 위 분석을 통하여, 72%의 트리글리세라이드가 소모되며, 회수 유기용액내의 지방산 알킬에스테르/지방산 에스테르 글리세린 카보네이트의 비(M)가 12임을 알 수 있었다.Into a 500 ml reactor equipped with a reflux condenser and a stirrer, 90 g of triglyceride extracted from soybean and 1 g of sulfuric acid (98%) as a catalyst were injected. Subsequently, after adding 64 g of methyl alcohol and 90 g of dimethyl carbonate, the temperature of the reactor was maintained at 90 ° C., methyl alcohol was refluxed, and the reaction was continued for 4 hours. After 4 hours, the reaction was terminated, the reaction solution was placed in a separatory funnel, and the lipophilic organic liquid obtained by removing the catalyst and glycerin carbonate using distilled water was used to remove the residual water with magnesium sulfate, followed by methyl alcohol and dimethyl carbonate. Distilled. The solution containing the finally recovered fatty acid methyl ester was subjected to purity analysis using a gas chromatography analyzer equipped with a non-polar microtube. Through the above analysis, 72% of triglyceride was consumed, and it was found that the ratio (M) of fatty acid alkyl ester / fatty acid ester glycerin carbonate in the recovered organic solution was 12.
실시예 2-25: 촉매에 따른 트리글리세라이드의 소모율과 M의 변화 Example 2-25 Triglyceride Consumption and M Changes with Different Catalysts
촉매의 종류를 달리한 것을 제외하고는, 실시예 1과 동일한 방법으로 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 제조하였다. 사용된 촉매와 트리글리세라이드의 소모율과 M값의 결과는 표 1에 나타난 바와 같다.A fatty acid alkyl ester and a fatty acid ester glycerin carbonate were prepared in the same manner as in Example 1, except that the type of catalyst was changed. The results of consumption and M value of the catalyst and triglyceride used are shown in Table 1.
상기 표 1에서 보듯이, 염기성 촉매하에서 높은 수득율과 큰 M값을 얻었다.As shown in Table 1, a high yield and a large M value were obtained under a basic catalyst.
실시예 26-30: 알코올의 종류에 따른 트리글리세라이드의 소모율과 M값의 변화 Example 26-30 : Changes in Triglyceride Consumption and M Values According to Alcohol Types
촉매로 MeONa를 사용하고, 알코올의 종류를 달리하는 것을 제외하고는, 실시예 18과 동일한 상태에서 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 제조하였다. 사용된 알코올과 트리글리세라이드의 소모율과 M값은 표 2에 나타난 바와 같다.A fatty acid alkyl ester and a fatty acid ester glycerin carbonate were prepared in the same manner as in Example 18 except that MeONa was used as a catalyst and the type of alcohol was changed. The consumption and M values of the alcohol and triglycerides used are shown in Table 2.
상기 표 2에서 보듯이, 알코올의 탄화수소가 지방족일때 높은 수득율과 M값을 얻었다.As shown in Table 2, when the hydrocarbon of the alcohol is aliphatic, high yields and M values were obtained.
실시예 31-33: 트리글리세라이드의 종류에 따른 트리글리세라이드의 소모율과 M값의 변화 Example 31-33 : Changes in Triglyceride Consumption and M Values According to Types of Triglycerides
트리글리세라이드의 종류를 팜유, 해바라기 기름 또는 피마자 기름을 사용하는 것을 제외하고는, 실시예 18과 동일한 상태에서 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 제조하였으며, 실험결과는 표 3에 나타난 바와 같다.A fatty acid alkyl ester and a fatty acid ester glycerin carbonate were prepared in the same state as in Example 18, except that palm oil, sunflower oil, or castor oil were used as the kind of triglyceride, and the experimental results are shown in Table 3.
상기 표 3에서 보듯이, 트리글리세라이드의 종류에 관계없이 높은 수득율과 M값을 얻었다.As shown in Table 3, a high yield and M value were obtained regardless of the type of triglyceride.
실시예 34-36: 메틸 알코올의 양에 따른 트리글리세라이드의 소모율과 M값의 변화 Example 34-36 : Changes in Triglyceride Consumption and M Values According to the Amount of Methyl Alcohol
메틸 알코올의 양을 달리하는 것을 제외하고는, 실시예 18과 동일한 상태에서 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 제조하였으며, 메틸알코올 양에 따른 실험결과는 표 4에 나타난 바와 같다.Except for varying the amount of methyl alcohol, fatty acid alkyl ester and fatty acid ester glycerin carbonate was prepared in the same state as in Example 18, the experimental results according to the methyl alcohol amount is shown in Table 4.
상기 표 4에서 보듯이, 메틸 알코올의 양이 많을수록 높은 수득율과 M값을얻었다.As shown in Table 4, the higher the amount of methyl alcohol obtained a higher yield and M value.
실시예 37-39: MeONa 촉매의 양에 따른 트리글리세라이드의 소모율과 M값의 변화 Example 37-39 Changes in Triglyceride Consumption and M Values According to the Amount of MeONa Catalyst
MeONa 촉매의 양을 달리하는 것을 제외하고는, 실시예 18과 동일한 상태에서 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 제조하였으며, 촉매량 변화에 따른 실험결과는 표 5에 나타난 바와 같다.Except for varying the amount of MeONa catalyst, fatty acid alkyl ester and fatty acid ester glycerin carbonate were prepared in the same state as in Example 18, and the experimental results according to the change in catalyst amount are shown in Table 5.
상기 표 5에서 보듯이, 촉매의 양이 많을수록 높은 수득율과 M값을 얻었다.As shown in Table 5, the higher the amount of the catalyst, the higher yield and M value were obtained.
실시예 40-41: 온도에 따른 트리글리세라이드의 소모율과 M값의 변화 Example 40-41 : Change of Triglyceride Consumption and M Values with Temperature
온도를 달리하는 것을 제외하고는, 실시예 18과 동일한 상태에서 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 제조하였으며, 온도 변화에 따른 실험결과는 표 6에 나타난 바와 같다.Except for changing the temperature, fatty acid alkyl ester and fatty acid ester glycerin carbonate was prepared in the same state as in Example 18, and the experimental results according to the temperature change are shown in Table 6.
상기 표 6에서 보듯이, 온도가 높을수록 높은 수득율과 M값을 얻었다.As shown in Table 6, the higher the temperature, the higher yield and M value were obtained.
실시예 42-44: 유기 카보네이트의 종류에 따른 트리글리세라이드의 소모율과 M값의 변화 Example 42-44 Changes in Triglyceride Consumption and M Values According to Organic Carbonate Types
유기카보네이트의 종류를 달리하는 것을 제외하고는, 실시예 18과 동일한 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 제조하였으며, 유기카보네의 종류에 따른 실험결과는 표 7에 나타난 바와 같다.Except for varying the type of organic carbonate, the same fatty acid alkyl ester and fatty acid ester glycerin carbonate as in Example 18 was prepared, and the experimental results according to the type of organic carbonone are shown in Table 7.
상기 표 7에서 보듯이, 디에틸 카보네이트와 디페닐 카보네이트가 높은 수득율과 M값을 얻었다.As shown in Table 7, diethyl carbonate and diphenyl carbonate obtained high yields and M values.
이상에서 상세히 설명하고 입증하였듯이, 본 발명은 알코올에 트리글리세라이드와 유기 카보네이트를 용해시키고, 균질촉매, 합성 지오라이트 촉매, 이온교환수지 촉매 또는 4가 알킬 암모늄염 촉매를 첨가하여 반응시켜, 지방산 알킬에스테르와 지방산 에스테르 글리세린 카보네이트를 동시에 제조하는 방법을 제공한다. 본 발명에 의하면, 비독성, 비휘발성의 지방산 알킬에스테르를 간단한 공정으로 경제적, 효율적으로 생산할 수 있으며, 계면활성이 적은 전기 화합물의 효능을 향상시키기 위해 이용되는 분산제로서 환경친화적인 지방산 에스테르 글리세린 카보네이트를 동시에 제조할 수 있다.As described and demonstrated in detail above, the present invention dissolves triglycerides and organic carbonates in alcohol, and reacts by adding a homogeneous catalyst, a synthetic zeolite catalyst, an ion exchange resin catalyst or a tetravalent alkyl ammonium salt catalyst to react with a fatty acid alkyl ester. Provided are methods for the simultaneous preparation of fatty acid ester glycerin carbonate. According to the present invention, a non-toxic, nonvolatile fatty acid alkyl ester can be produced economically and efficiently in a simple process, and an environmentally friendly fatty acid ester glycerin carbonate is used as a dispersant used to improve the efficacy of an electric compound having low surfactant activity. It can be produced at the same time.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통The specific parts of the present invention have been described in detail above.
상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시태양일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.For those skilled in the art, it will be apparent that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (12)
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| JPH02279653A (en) * | 1989-04-18 | 1990-11-15 | Kao Corp | Production of glycerol mono-fatty acid ester |
| WO1998056747A1 (en) * | 1997-06-10 | 1998-12-17 | Universidad Politecnica De Valencia | Process and catalysts for the selective production of esters of fatty acids |
| US5872268A (en) * | 1995-12-13 | 1999-02-16 | Mitsubishi Chemical Corporation | Process for preparing salt of fatty acid ester of hydroxycarboxylic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH02279653A (en) * | 1989-04-18 | 1990-11-15 | Kao Corp | Production of glycerol mono-fatty acid ester |
| US5872268A (en) * | 1995-12-13 | 1999-02-16 | Mitsubishi Chemical Corporation | Process for preparing salt of fatty acid ester of hydroxycarboxylic |
| WO1998056747A1 (en) * | 1997-06-10 | 1998-12-17 | Universidad Politecnica De Valencia | Process and catalysts for the selective production of esters of fatty acids |
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